Lubricating oil containing a reaction product of p2s5-terpene and 2.4.6-trialkylphenol



Patented July 20, 1954 2,684,334

UNITED STATES PATENT OFFICE LUBRICATING OIL CONTAINING A REAC- TIONPRODUCT F PzSs-TERPENE AND 2.4.6-TRIALKYLPHENOL Julian G. Ryan andGeorge L. Hayes, Wood River, 111., assignors to Shell DevelopmentCompany, Emeryville, Calif., a corporation of Delaware No Drawing.Application May 25, 1951, Serial No. 228,356

15 Claims. (01. 252-4613) 1 2 This invention relates to improvedlubricating oycloalkyl hydrocarbon radicals containing if decompositionsparticularly for use in aviation and sired minor proportions of polarsubstituents, similar types of engines. e. g, N02, NHz, OH, SOsH, COOH,CN, etc, Y

The problem of engine fOul Corrosion and is a chalcogen element havingan atomic number the like, is particularly acute in aviation engines, 5of 8 to 16, namely, oxygen and sulfur (yielding in which the hightemperatures developed in the the phenols and thiophenols), the radicals(Yl-l) cylinders tend to act upon lubricating oils to being attacheddirectly to the aromatic ring, a: cause the deposition of resinous andVarnish-lik is an integer of 1 to 2 and y is an integer of at productson the pistons and elsewhere and to least 3. If a: is greater than one,then the radiproduce lacquer-like coatings and carbonaceous 10 cans YHan b th same or diff rent,

materials, which in time tend to cause ring and A preferred embodimentof additives within the valve sticking and interfere with engineoperaclass as broadly defined by formula I are 2,4,6, tion. High pistontemperatures in aviation entrisubstituted phenols represented by theformula:

gines promote the formation of deposits which, in turn, aggravate thesituation by reducing the heat transfer. Furthermore, fuel residues from1 R2 incomplete combustion of fuel contribute to the deposition oflacquer-like and carbonaceous materials in the engine. (11) Accordingly,it is an object of this invention to provide lubricating oilcompositions which have whetaem R1 15 a ternary alkyl radlcal such asimproved properties in one or more of the followg i g g igg i ua thy:-ll Y an e 1.6, pre era y (3011 all'llng up 0 ing qualities. hightemperature detergency, de about 12 carbon atoms, one of R2 and R3 is ae ti n, corcreased plston rmg Stlckmg wear I due 0 3 hydrocarbonradical, preferably an alkyl radical,

rosion resistance, stability in presence of copper a n in an the eithera primary, secondary or tertiary alkyl radior crankcase catalyst Oxld noStab d cal, while the other one is the same or different like. Anotherpurpose is to produce a superior W heavy duty lubricant particularlysuitable for use i s g fgggg fifg fi 55 325 g ifi ggfi g z in aircraftand other interna1 combustion engines grtho or p y y 1 pi y g Operatingat relgtlvely .hlgh cylmder temperw alkyl (ortho-hydroXy-a1kyl benzy1-)radical betures. Other ob ects will be apparent from the mg theOrthodsomm' when it is R2 d the para? ggfg g gg found that suchlubricating isomer when it is Rs. When R2 or R3 is an orthob 1 co b theor para-hydroxy-alkyl phenyl-subst1tuted alkyl problems can 8 substa w Wover me y radical, respectively, the alkyl substituents therein ororation in a lubricatin oil base, of minor s2", i but in criticalmutually coacting of are chosen to be identical with R1 and the otherone of R2 and R3; thus, the compounds are proportions, of two particulartypes of non-ashforming additives, the combination of which withalkylezte blsmlkylphenom' the base lubricant exerts a synergisticeffect, re- Speclfic examples of compqunds represented by sultin in acomposition of outstanding stability 4 formula and 4 9 particularly andlubricity useful in the practice of this invention are:

One Of the additives Of the combination is a 2 t t b t 1 4 th 1 1 2,4,6trisubstituted polar containing aromatic ZA-ditertiarybutyl-fi-methylphenol compound represented by the general formula: 2,4dimethy1 6 tertia1.y buty1phem1 2,6-di-sec-butyl-fi-tertiary butylphenol(R)yAr YHM (I) 2,4-di-n-buty1-G-tertiary-octylphenol wherein Ar is amonoor dinuclear aromatic 2,6-ditertiary-butyl-4-benzylphenol radical, Ris the same or different organic radi-2,6-ditertiary-amyl-d-methylphonol cals attached to nuclear carbonatoms, at least 2, i-ditertiary-amy16-methylphenol one of said Rs beingan alkyl radical ortho in '2,4,6-tritertiary-butylphenol position to aYI-I radical and linked to the ring2,6-ditertiary-.buty1-4-methylthiophenol carbon atom by a tertiarycarbon in the alkyl 2,4-ditertiary-butyl-6-methylthiopheno1 group andthe remaining Rs being the same as2,e-dimethyl-6-tertiary-butylthiophenol the R which is ortho to YHradical or they can 2,4-dimethy1-6-tertiary-octylthiophenol be the sameor different essentially alkyl, aralkyl,2,5-ditertiary-amyl-4-methylthiophenol 2,4,6-tritertiary-amylthiophenol2,2 methylene bis 4 methyl 6 tertiarybutylphenol) 2,2 -methylene bis(4,6-ditertiary-butylphenol 2,2-methylenebis(4,6-ditertiary-octylphenol) 2,2 methylene bis(4 methyl 6tertiaryamylphenol) 2,2 methylene, bis(4 methyl 6 tertiaryoctylphenol)2,2 methylene bis(4 methyl 6 tertiarybutylthiophenol) 2,2-methy1enebis(4 octyl-6-tertiary-butylthiophenol) 2,2 methylene bis(4,6 ditertiarybutylthiophenol) 2,2 methylene bis(4,6 ditertiary amylthiophenol) 2,2methylene amylthiophenol) 2,2 methylene bis(4 methyl 6tertiaryoctylthiophenol) (2 hydroxy 3 tertiary butyl 5 methylphenyl)-furylmethane (2 hydroxy 5 tertiary butylphenyl) furylmethane 1,1 bis(2hydroxy 3 tertiary butyl 5- methylphenyl) isobutane Bis(2 hydroxy 3tertiary butyl 5 methylphenyl) phenylmethane 2,2 bis(2 hydroxy 3tertiary butyl 5- methylphenyl) propane 2,2 bis(2 hydroxy 3 tertiarybutyl 5- methylphenyl) butane bis(4 methyl 6 tertiary- Thetrisubstituted phenolic compounds and mixtures thereof can be used inamounts varying from 0.01 to about and preferably from 0.1 to 5% byweight, with from 0.5% to 3% by weight being a still more preferredrange.

The second additive used in lubricating compositions of this inventionis a phosphorized terpene compound obtained as a reaction product byreacting a terpene compound with a phosphorizing agent. Terpenessuitable for producing reaction products of this invention includealphaand beta-pinene, dipentene, terpinolene, menthene, alpha-terpineol,camphene, limonene, turpentine, pine oil, camphor oil, terpenes obtainedas a by-product in manufacture of synthetic camphor, carene, fenchene,terpinene, diterpenes, camphoric acid, abietic acid, etc. Thephosphorizing agents which can be used to form reaction products of thisinvention are: P285, P483, P2S85, P2863, P, P205, POCls, PCls, PC15,PSC13, etc. Also the terpene compounds can be first reacted with asulfurizing agent, e. g. 8012, S2C12, sodium polysulfide, 8eCl2, 8eCl4and the like and thereafter retreated with a phosphorizing agent, e. g.P205, P285, phosphoric acid, etc., so that the final reaction productcontains both sulfur and phosphorus. If desired, the reaction can becarried out in the reverse order, namely, the terpene compound can befirst treated with a phosphorizing agent, e. g., P205 and thereaftertreated with sulfur, metal polysulfides, sulfur chloride and the like.The reaction can be carried out in an inert diluent such as lighthydrocarbons, or in a base oil to which the reaction product is intendedto be added.

When the reaction products of this invention are produced in a two-stepprocess, namely, by first sulfurizing and then phosphorizing, thesulfurization temperature can vary from 200 to 400 F. and thephosphorization step can be carried out at the reflux temperature of thereactants.

4 With phosphorus sulfides the reaction can be made to proceed at roomtemperature or higher temperatures depending upon the terpene compoundbeing treated.

The mole ratio of the terpene compounds to the phosphorus and sulfur orphosphorizing reagent may vary over wide limits, such as from 10:1,preferably 4:1, to 3:1 moles of the abovementioned reagents,respectively.

The preparation of the reaction products can be efi'ected by heating aterpene compound to an elevated temperature of around 200 F. or higherand slowly adding the phosphorizing agent. After the addition iscompleted, the temperature of the reaction is increased to 250-400 F.and preferably is maintained between 300 and 350 F. until all of thephosphorizing agent such as P285 has reacted and evolution of hydrogensulfide ceases. If desired, the reaction product can be purified orrefined by solvent treatment or neutralized by treatment with a nitrogenbase.

It is preferred to utilize the phosphorized and sulfurized terpenecompound, as such, in the present compositions. However, they can beneutralized and/or reacted with organic nitrogen base compounds such asamines and quaternary ammonium compounds, as illustrated bytriamylamine, triethanolamine, laurylamine, octadecylamine, morpholine,dibutylamine, dicyclohexylamine, trimethylhexylammonium hydroxide,dibenzylamine, methylaniline, trimethylbenzylammonium hydroxide,piperidine, and the like.

Specific examples of reaction products under discussion and theirdetailed method of preparation are as follows:

About 4 moles of gum spirits of terpentine was heated under agitation toaround 250 F., and about 1 mole of P285 was added portionwisemaintaining the temperature of the mixture around 250 F. until all ofthe P285 had been added. The temperature was then increased to 275-300F. and the mixture reacted until evolution of H28 ceased. On analysisthe product contained 12.8% S and 4.81% P.

Another product was prepared by heating 4 moles of alpha-pinene with 1mole of P285 at around 240 F. until all of the P285 had been added andthereafter increasing the reaction temperature to around 300 F. andmaintaining the mixture at said temperature until the reaction wascompleted. On analysis the product contained 12.7% 8 and 4.62% P.

The above reaction products can be modified by treating them with aminesof which the long chain alkyl amines, e. g., octadecylamine andlaurylamine, are preferred.

The phosphorized-terpene compound reaction product can be used inamounts varying from 0.01 to 10% and preferably between 011 and 5% byweight, with from 0.5% to 1.0% representing a still more preferredrange.

The base for *additives of this invention can be any natural orsynthetic material having lubricating properties. Thus, the base may bea hydrocarbon oil of wide viscosity range, e. g., SUS at 100 F. to SUSat 210 F. The hydrocarbon oils may be blended with fixed oils such ascastor oil, lard oil and the like, and/or with synthetic lubricants suchas polymerized olefins, copolymers of alkylene glycols and oxides;organic esters of polybasic organic and inorganic acids, e. g.,di-2-ethy1hexyl sebacate, dioctyl phthalate, trioctyl phosphate;polymeric tetra-' hydrofuran; polyalkyl silicone polymers, e. g.,dimethyl silicone polymer and the like. If desired, the syntheticlubricants may be used as the sole base lubricant or admixed with fixedoils and their derivatives.

Lubricating compositions of this invention are particularly useful inaviation engines operating on leaded fuels containing a halohydrocarbonscavenger such as ethylene dibromide, with or without the presence of anorganic phosphate, e. g., tricresylphosphate.

Illustrative examples of final compositions of this invention in arefined mineral oil base having the properties as indicated below areset forth as Compositions A-J.

PROPERTIES OF THE BASE MINERAL OIL Gr., API 28.5 Color, NPA 4 Pourpoint, F Flash, F 4'70 Fire, F 560 Visc. at 100 F., SSU 1239 Visc. at210 F., SSU 99.5 Viscosity index 96 Carbon residue, per cent wt.(Conradson) 0.32

Ash, per cent wt None Sulfur, per cent wt 0.13 Specific dispersion 109Composition A Per cent Pass-turpentine reaction product 0.82,6-ditert-butyl-4-methylphenol 1 Mineral lubricating oil Balance Theproperties of this composition are:

Gr., API 28.3 Color, NPA 5 Pour point, F 10 Flash, F 470 Fire, F 560Vis. at 100 F., SSU 1150 Vis. at 210 F., SSU 95 Viscosity index 95Carbon residue, per cent wt. (Conradson) 0.32 Ash None Sulfur 0.16Specific dispersion 110.6

Composition B Per cent Past-turpentine reaction product 0.52,6-ditert-butyl-4-methylphenol 1 Mineral lubricating oil BalanceComposition C Per cent Past-turpentine reaction product 0,252,6-ditert-butyll-methylphenol 1 Mineral lubricating oil BalanceComposition D Per cent Pass-turpentine reaction product 0.82,S-ditert-butyl-4-methylphenol '8 Mineral lubricating oil BalanceComposition E Per cent Pzss-pinene reaction product 0.8

2,6-ditert-butyl-4-methylphenol l 1 Mineral lubricating oil BalanceComposition F Per cent PzS5-pinene reaction product; 0.5

2,6-ditert-butyl-4-methylphenol 1 Mineral lubricating oil Balance 6Composition G Per cent PzSs-pinene reaction product 0.252,6-ditert-butyl-4-methylphenol 1 Mineral lubricating oil BalanceComposition H Per cent PZSE-pinene reactionv product 0.82,S-ditert-butyl-4-methylphenol 3 Mineral lubricating oil BalanceComposition I Per cent Pass-turpentine reaction product 0.82,2'-methylene bis(4-methyl-6-tert-butylphenol) 1 Mineral lubricatingoil Balance Composition J Per cent P2S'5pinene reaction product 0.82,2-methylene bis(4-methyl-6-tert-butylphenol) 1 Mineral lubricating oilBalance To illustrate the pronounced improvement obtained usinglubricating. compositions of this invention in aircraft engines thefollowing tests were made and the data are presented in the table.

I. Compositions of this invention were tested in a Pratt and Whitney3-4360 single-cylinder engine in accordance with the procedure outlinedby the Pratt and Whitney Aircraft Corporation for evaluating cokingtendency of piston engine lubricating oils by noting the resistance ofthe oil to high temperature oxidation by temperature stressing the testoil in the exhaust rocker box of an R-4360 cylinder.

11,. Compositions of this invention were also tested in a COT engine,developing 8 horsepower at 2400 R. P. M. for hours at the end of whichtime the condition of the engine was examined and rated.

111. Compositions of this invention were also subjected to the Dornteoxidation test as described in the Industrial and Engineering Chemistry28, page 26 (1936).

TABLE.--TEST RESULTS Dornte oxidation test [1800 cc., time-minutes, Cuand Fe catalyst] Composition Cu Cat. Fe Cat.

Mineral oil Mineral oil 1% 2.6-ditert-butyl-4-methylphenol 400 340Mineral oil 25% PiSi-terpene reaction product 480 l, 480 Composition A680 2, 480 Composition E 680 2,480

Cooperative oil test, CRC project number CLEO-40-46 [Engine (80 hoursgeneral performance test) D Total Bearing Composition Engine wt. lossRating (Mg.)

Mineral oil .L "12 l, 758 Mineral oil 1%2,G-ditert-butyI-i-inethylphenol 60 1, 555 Mineral oil 25% PzS -terpenereaction produ 1,502 Composition B 87 38 Composition F 89 24 CompositionH 76 33 '100=perfect; 50=fair; 0=very poor. {Operation stopped beforethe 80-hour test because of excess engine fouling.

*Composition Y=Commcrcial compounded aviation oil containing Zn salt ofalkyl salicylic acid.

{*Composition XX Mineral oil 1% 2,6-ditert-butyl-4-methylp cm e 10perfect; very poor.

' Thus, the present invention provides outstanding non-ash-forminglubricating oils for use in aviation engines, which lubricating oilsconsist essentially of a lubricating oil containing a minor amount eachof certain alkylphenols and of a phosphorized-, sulfurized-terpene, tothe essen tial exclusion or" other materials. Although the preferredcompositions consist essentially of the three components specified, theaddition of minor amounts of other additives is advantageous in someapplications, additives such as blooming agents, pour point depressantsor viscosity improvers, extreme pressure agents, anti-foaming agents andthe like. Among the specific additives which can be'used are oil-solublenon-ashforming salts of various nitrogen bases with detergent-formingacids. Organic bases include various nitrogen bases as primary,secondary, tertiary amines and quaternary ammonium bases.

Examples of detergent-forming acids are the various fatty acids of sayto 30 carbon atoms, wool fat acids, paraffin wax acids (produced byoxidation of paraifin Wax), chlorinated fatty acids, rosin acids,aromatic carboxylic acids including aromatic fatty acids, aromatichydrcxy fatty acids, parafiin wax benzoic acids, various alkyl salicylicacids, phthalic acid mono-esters, aromatic keto acids, aromatic etheracids, and the like.

Extreme pressure agents which may be used comprise: neutral aromaticsulfur compounds of relatively high boiling temperatures such as diarylsulfides, diaryl disulfides, alkyl aryl disulfides, e. g., diphenylsulfide, diphenol sulfide, dicresol sulfide, dixylenol sulfide, methylbutyl diphenol sulfide, dibenzyl sulfide, corresponding diandtri-sulfides, and the like: sulfurized fatty oils or esters of fattyacids and monohydric alcohols, e. g., sperm oil, jojaba oil, etc.; inwhich the sulfur is strongly bonded, sulfurized long-chain olefins suchas may be obtained by dehydrogenation or cracking of wax;sulfurized-phosphorized fatty oils or acids, phosphorus acid estershaving sulfurized organic radicals, such as esters of phosphorus orphosphoric acids with sulfurized hydroxy fatty acids; chlorinatedhydrocarbons, such as chlorinated parafiin, aromatic hydrocarbons andchlorinated esters of fatty acids containing the chlorine in other thanthe alpha position.

Additional ingredients may comprise oil-soluble urea or thioureaderivatives, e. g., urethanes, allophanates, carbazides, carbazones,etc., poiyisobutylene polymers, unsaturated polymerized esters of fattyacids and monohydric alcohols and other high molecular weightoil-soluble compounds.

Depending upon the additive used and conditions under which it is used,the amount of additive used may vary from 0.01 to 2% or higher. However,substantial improvement is obtained by using amounts ranging from 0.1 to0.5% in combination with the two primary additives of this invention.

Compositions of this invention may also be used with motor oils, turbineoils, steam cylinder oils, marine engine oils, refrigeration oils, andused for various lubricating purposes other than engine lubrication,such as slushing and flushing oils, rust inhibiting oils, quenching anddrawing oils, greases, wax compositions, and the like.

We claim as our invention:

1. A non-ash aviation engine lubricating oil composition having thefollowing formulation:

2,6 ditertiarylbutyl-4-methylphenol 1 Reaction product ofPzSs-turpentina 0.8 Mineral lubricating oil Balance 2. A non-ashcontaining lubricating oil composition for aviation engines consistingessentially of a mineral lubricating oil having incorporated thereinfrom about 0.5 to 1% of a reaction product of Pzss-turpentine and fromabout 0.5 to 3% of 2,2-'nethylene bis(i-methyl-S-tertiarybutylphenol).

8. A non-ash containing lubricating oil composition for aviation enginesconsisting essentially of a mineral lubricating oil having incorporatedtherein from about 0.5 to 1 of a reaction product of Pzss-pinene andfrom about 0.5 to 3% of 2,2- methylene bis(4 methyl-o-tertiarybutylphenol).

4. A non-ash containing lubricating oil composition for aviation enginesconsisting essentially of a mineral lubricating oil having incorporatedtherein from about 0.5 to 1% of a reaction prod net of PzSa-pinene andfrom about 0.5 to 3% of 2,6-ditertiarybutyll-methylphenol.

5. A non-ash containing lubricating oil composition for aviation enginesconsisting essen tially of a mineral lubricating oil having incorporatedtherein from about 0.5 to 1% of a reaction product of Pass-turpentineand from about 0.5 to 3% of 2,6-ditertiarybutyl-4methylphenol.

6. A non-ash containing lubricating oil composition for aviation enginesconsisting essentially of a mineral lubricating oil having incorporatedtherein from about 0.1 to 5% each of a reaction product of Pzss-pineneand of 2,6-ditertiarybutyll-methylphenol.

7. A non-ash containing lubricating oil composition for aviation enginesconsisting essentially of a mineral lubricating oil having incorporatedtherein from about 0.1 to 5% each of a reaction product ofPass-turpentine and of 2,6- ditertiarybutyl-4-methylphenol.

8.A non-ash containing lubricating oil composition for aviation enginesconsisting essentially of a mineral lubricating oil having incorporatedtherein from about 0.1 to 5% each of a reaction product of PzSs-pineneand of 2,4,6- trialkylphenol, at least one of the alkyl radicals orthoto the hydroxyl group being a tertiary alkyl radical.

9. A non-ash containing lubricating oil composition for aviation enginesconsisting essentially of a mineral lubricating oil having incorporatedtherein from about 0.1 to 5% each of a a reaction product ofPass-turpentine and of 2,4,6-trialkylphenol, at least one of the alkylradicals ortho to the hydroxyl group being a tertiary alkyl radical.

10. A non-ash containing lubricating oil composition for aviationengines consisting essentially of a mineral lubricating oil havingincorporated therein from about 0.1 to 5% each of a reaction product ofPzss-terpene and of 2,4,6- trialkylphenol, at least one of the alkylradicals ortho to the hydroxyl group being a tertiary alkyl radical.

11. A non-ash containing lubricating oil composition for aviationengines consisting essentially of a mineral lubricating oil havingincorporated therein from about 0.1 to 5% each of a reaction product ofPzSs-turpentine and of 2,2- methylene bis(e-alkyl-6-tertiaryalkvlpheno1) 12. A non-ash containing lubricating oilcomposition for aviation engines consisting essentially of a minerallubricating oil having incorpoporated therein from about 0.1 to 5% eachof a reaction product of Pass-turpentine and of 2,2- alkylidenebis(4-alkyl-G-tertiaryalkylphenol) 13. A non-ash containing lubricatingoil composition for aviation engines consisting essentially of a minerallubricating oil having incorporated therein from about 0.1 to 5% each ofa reaction product of PzSs-terpene and or" 2,2-alky1- idenebis(4-alkyl-6-tertiaryalkylphenol) 14. A non-ash containing lubricatingoil com- Iii position for aviation engines consisting essentially of amineral lubricating oil having incorporated therein from about 0.1 to 5%each of a phoshporus sulfide-terpene reaction product and of atrisubstituted phenol selected from the group consisting of2,4,6-trialkylphenol, at least one of the alkyl radicals thereof orthoto the hydroxyl group being a tertiary alkyl radical and 2,2-alkylidenebis( i-alkyl-G-tertiaryalkylphenol) 15. A non-ash containing lubricatingoil composition for aviation engines comprising a mineral lubricatingoil having incorporated therein 0.8% of a reaction product of pinenewith P235 and 1% of 2,6-ditertiary-butyl-4-methyl phenol.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,257,872 Trautman Oct. '7, 1941 2,486,188 May Oct. 25, 19492,489,249 Adelson Nov. 29, 1949 2,493,217 Berger Jan. 3, 1950

10. A NON-ASH CONTAINING LUBRICATING OIL COMPOSITION FOR AVIATIONENGINES CONSISTING ESSENTIALLY OF A MINERAL LUBRICATING OIL HAVINGINCORPORATED THEREIN FROM ABOUT 0.1 TO 5% EACH OF A REACTION PRODUCT OFP2S5-TERPENE AND OF 2,4,6TRIALKYLPHENOL, AT LEAST ONE OF THE ALKYLRADICALS ORTHO TO THE HYDROXY GROUP BEING A TERTIARY ALKYL RADICAL.